U.S. patent application number 10/559451 was filed with the patent office on 2006-07-27 for polymethine ethers.
Invention is credited to Keiki Chichiishi, Shigeo Fujita, Nobuaki Sasaki, Sayuri Wada.
Application Number | 20060167272 10/559451 |
Document ID | / |
Family ID | 33549531 |
Filed Date | 2006-07-27 |
United States Patent
Application |
20060167272 |
Kind Code |
A1 |
Sasaki; Nobuaki ; et
al. |
July 27, 2006 |
Polymethine ethers
Abstract
The invention provides novel compounds useful as intermediates
for the production of polymethine compounds containing a desired
counter ion with high purity and in high yields. Thus provided are
polymethine ether compounds of the general formula (I) given below
and a method of producing polymethine compounds which comprises
bringing those compounds into contact with an acid. ##STR1## In the
above formula, R represents an alkyl group, an alkoxyalkyl group or
an aryl group which may optionally be substituted, R.sub.1 and
R.sub.2 each independently represents a hydrogen atom, halogen
atom, nitro group, alkyl group, alkoxyalkyl group, alkoxy group or
alkoxyalkoxy group and R.sub.1 and R.sub.2 may be bound to each
other to form a ring; R.sub.3 represents an alkyl group, which may
optionally be substituted; L is an alkylene group required for the
formation of a ring structure; and X represents a hydrogen atom,
halogen atom, alkoxy group, aryloxy group, alkylthio group,
arylthio group or substituted amino group.
Inventors: |
Sasaki; Nobuaki; (Yao-shi,
JP) ; Chichiishi; Keiki; (Yao-shi, JP) ; Wada;
Sayuri; (Yao-shi, JP) ; Fujita; Shigeo;
(Yao-shi, JP) |
Correspondence
Address: |
BIRCH STEWART KOLASCH & BIRCH
PO BOX 747
FALLS CHURCH
VA
22040-0747
US
|
Family ID: |
33549531 |
Appl. No.: |
10/559451 |
Filed: |
June 16, 2004 |
PCT Filed: |
June 16, 2004 |
PCT NO: |
PCT/JP04/08794 |
371 Date: |
December 5, 2005 |
Current U.S.
Class: |
548/455 ;
548/465 |
Current CPC
Class: |
C07D 209/34 20130101;
C07D 209/94 20130101; C07D 209/10 20130101; C09B 23/0066
20130101 |
Class at
Publication: |
548/455 ;
548/465 |
International
Class: |
C07D 405/14 20060101
C07D405/14; C07D 403/02 20060101 C07D403/02 |
Foreign Application Data
Date |
Code |
Application Number |
Jun 25, 2003 |
JP |
2003-181590 |
Claims
1. A polymethine ether compound represented by the general formula
(I): ##STR15## wherein R represents an alkyl group, an alkoxyalkyl
group or an aryl group which may optionally be substituted, R.sub.1
and R.sub.2 each independently represents a hydrogen atom, halogen
atom, nitro group, alkyl group, alkoxyalkyl group, alkoxy group or
alkoxyalkoxy group and R.sub.1 and R.sub.2 may be bound to each
other to form a ring; R.sub.3 represents an alkyl group, which may
optionally be substituted; L is an alkylene group required for the
formation of a ring structure; and X represents a hydrogen atom,
halogen atom, alkoxy group, aryloxy group, alkylthio group,
arylthio group or substituted amino group.
2. A polymethine ether compound according to claim 1, wherein R is
an alkyl group containing 1-8 carbon atoms, an alkoxyalkyl group
containing 2-8 carbon atoms in total or a phenyl which may
optionally have an alkyl group containing 1-4 carbon atoms or an
alkoxy group containing 1-4 carbon atoms as a substituent, R.sub.1
and R.sub.2 each is a hydrogen atom, an alkyl group containing 1-8
carbon atoms, an alkoxyalkyl group containing 2-8 carbon atoms in
total or an alkoxy group containing 1-8 carbon atoms or R.sub.1 and
R.sub.2 are bound to each other and form, together with the benzene
ring carbon atoms bound to R.sub.1 and R.sub.2, respectively, a
benzene ring, a hydrocarbon ring containing 5-7 carbon atoms or an
oxygen-containing heterocycle containing 3-6 carbon atoms, and
R.sub.3 is an alkyl group containing 1-18 carbon atoms or an
alkoxyalkyl group containing 2-8 carbon atoms in total.
3. A polymethine ether compound according to claim 1, wherein L is
an alkylene group containing 2-4 carbon atoms.
4. A polymethine ether compound according to claim 1, wherein X is
a hydrogen atom, Cl, Br, an alkoxy group containing 1-8 carbon
atoms or a diphenylamino.
5. A method of producing polymethine compounds represented by the
general formula (IV) given below which comprises reacting a
polymethine ether compound represented by the general formula (I)
given above with an acid: ##STR16## wherein R.sub.1 and R.sub.2
each independently represents a hydrogen atom, halogen atom, nitro
group, alkyl group, alkoxyalkyl group, alkoxy group or alkoxyalkoxy
group and R.sub.1 and R.sub.2 may be bound to each other to form a
ring; R.sub.3 represents an alkyl group, which may optionally be
substituted; L is an alkylene group required for the formation of a
ring structure; X represents a hydrogen atom, halogen atom, alkoxy
group, aryloxy group, alkylthio group, arylthio group or
substituted amino group; and Z.sup.- represents an acidic
residue.
6. A polymethine ether compound according to claim 2, wherein L is
an alkylene group containing 2-4 carbon atoms.
7. A polymethine ether compound according to claim 2, wherein X is
a hydrogen atom, Cl, Br, an alkoxy group containing 1-8 carbon
atoms or a diphenylamino.
8. A polymethine ether compound according to claims 3, wherein X is
a hydrogen atom, Cl, Br, an alkoxy group containing 1-8 carbon
atoms or a diphenylamino.
Description
TECHNICAL FIELD
[0001] The present invention relates to novel polymethine ether
compounds and a method of producing polymethine compounds utilizing
the same.
BACKGROUND ART
[0002] In recent years, polymethine compounds have been in wide
use, among others, as light-to-heat converting agents for optical
recording media, for near-infrared absorbing filters or
plate-making materials for which laser beams are to be utilized.
These polymethine compounds generally form a salt structure with a
counter ion, and researches have been made concerning polymethine
compounds improved in various ways with respect to the counter ion
for the purpose of improving the solubility in solvents, the
compatibility with resins, the durability and the sensitivity to
laser beams.
[0003] For producing polymethine compounds containing a desired
counter ion species, a method is known which comprises once
synthesizing a polymethine compound containing a counter ion
species relatively easy to synthesize, for example a perchlorate
ion, tetrafluoroborate ion or p-toluenesulfonate ion, dissolving
the polymethine compound obtained and a compound containing the
desired counter ion species in a solvent, for example
dimethylformamide (hereinafter referred to as "DMF") to cause
counter ion species interchange in the solvent, as described in
Example 1 in Japanese Kokai Publication 2000-302992, for
instance.
[0004] Further, as is described in Example 1 in Japanese Kokai
Publication H11-1626, a synthetic method is known which comprises
once synthesizing a polymethine compound containing a counter ion
species relatively easy to synthesize, for example a perchlorate
ion, tetrafluoroborate ion or p-toluenesulfonate ion, reacting the
polymethine compound obtained with an alkali such as caustic soda
to give an intermediate compound (hereinafter referred to as
"hydroxy compound") resulting from elimination of the counter ion
and having a structure represented by the formula (B) given below,
and further reacting this hydroxy compound with a compound
containing the desired counter ion. ##STR2## (In the formula (B),
R.sub.1, R.sub.2, R.sub.3, L and X are as defined later herein
referring to the formula (I).)
[0005] However, as regards the former method, the range of
producible counter ion species is limited and, further, the counter
ion species exchange is incomplete and it is therefore difficult to
obtain, by that method, the high-purity compounds containing a
desired counter ion species in high yields. As for the latter
method, on the other hand, the hydroxy compounds are very unstable
and, therefore, this method of producing polymethine compounds
using those hydroxy compounds is not suitable as an industrial
production method since the purity and yield of the products are
low and a complicated purification process is required for
obtaining high-purity products.
[0006] As a compound structurally close to the polymethine ether
compounds of the invention, there is the compound (A) having the
structure shown below as described in Dyes and Pigments, 46 (2000),
164. However, there is no description about the use thereof, among
others. If the compound (A) is used to produce the corresponding
polymethine compound, the polymethine compound obtained will show
an absorption wavelength range fairly longer (.gtoreq.1000 nm) than
the general-purpose semiconductor laser wavelength range and,
further, the raw materials for the production thereof are special
and the production cost is increased accordingly, hence the
industrial use value will be restricted. ##STR3##
DISCLOSURE OF INVENTION
[0007] It is an object of the present invention to provide novel
polymethine ether compounds useful as intermediates for the
production of polymethine compounds containing a desired counter
ion.
[0008] As a result of various investigations made in an attempt to
accomplish the above object, the present inventors found that
certain novel polymethine ether compounds are stable and can be
handled with ease and when they are reacted with an acid,
high-quality polymethine compounds with an acidic residue as the
counter ion can be readily produced in high yields. This finding
has now led to completion of the present invention.
[0009] In a first aspect, the present invention provides
polymethine ether compounds represented by the following general
formula (I): ##STR4## wherein R represents an alkyl group, an
alkoxyalkyl group or an aryl group which may optionally be
substituted, R.sub.1 and R.sub.2 each independently represents a
hydrogen atom, halogen atom, nitro group, alkyl group, alkoxyalkyl
group, alkoxy group or alkoxyalkoxy group and R.sub.1 and R.sub.2
may be bound to each other to form a ring; R.sub.3 represents an
alkyl group, which may optionally be substituted; L is an alkylene
group required for the formation of a ring structure; and X
represents a hydrogen atom, halogen atom, alkoxy group, aryloxy
group, alkylthio group, arylthio group or substituted amino
group.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] FIG. 1 is an IR absorption spectrum of the polymethine ether
compound of Example 1.
[0011] FIG. 2 is an IR absorption spectrum of the polymethine ether
compound of Example 2.
[0012] FIG. 3 is an IR absorption spectrum of the polymethine ether
compound of Example 3.
[0013] FIG. 4 is an IR absorption spectrum of the polymethine ether
compound of Example 4.
[0014] FIG. 5 is an IR absorption spectrum of the polymethine ether
compound of Example 5.
[0015] FIG. 6 is an IR absorption spectrum of the polymethine ether
compound of Example 6.
[0016] FIG. 7 is an IR absorption spectrum of the polymethine ether
compound of Example 7.
[0017] FIG. 8 is an IR absorption spectrum of the polymethine
compound of Example 8.
DETAILED DESCRIPTION OF THE INVENTION
[0018] In the following, the present invention is described in
detail.
[Polymethine Ether Compounds]
[0019] First, the polymethine ether compounds represented by the
general formula (I) given below in accordance with the first aspect
of the invention are described. ##STR5## In the above formula, R
represents an alkyl group, an alkoxyalkyl group or an aryl group
which may optionally be substituted, R.sub.1 and R.sub.2 each
independently represents a hydrogen atom, halogen atom, nitro
group, alkyl group, alkoxyalkyl group, alkoxy group or alkoxyalkoxy
group and R.sub.1 and R.sub.2 may be bound to each other to form a
ring; R.sub.3 represents an alkyl group, which may optionally be
substituted; L is an alkylene group required for the formation of a
ring structure; and X represents a hydrogen atom, halogen atom,
alkoxy group, aryloxy group, alkylthio group, arylthio group or
substituted amino group. (Substituent R)
[0020] When R is an alkyl group, it is preferably a straight or
branched alkyl group containing 1-8 carbon atoms, particularly
preferably a straight or branched alkyl group containing 1-4 carbon
atoms. As examples, there may be mentioned methyl, ethyl, n-propyl,
isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl,
isopentyl, neopentyl, n-hexyl, isohexyl, sec-hexyl, 2-ethylbutyl,
n-heptyl, isoheptyl, sec-heptyl, n-octyl and 2-ethylhexyl.
[0021] When R is an alkoxyalkyl group, it is preferably one
containing 2-8 carbon atoms in total, particularly preferably one
containing 2-4 carbon atoms in total. As examples, there may be
mentioned methoxymethyl, 2-methoxyethyl, 3-methoxypropyl,
2-ethoxymethyl, 2-ethoxyethyl, 2-propoxyethyl and
2-butoxyethyl.
[0022] When R is an optionally substituted aryl group, it may be an
optionally substituted phenyl group or an optionally substituted
naphthyl group but preferably is an optionally substituted phenyl
group. Each substituent may be an alkyl, amino, nitro, alkoxy or
hydroxy group or a halogen atom, and preferably is an alkyl group
containing 1-4 carbon atoms or an alkoxy group containing 1-4
carbon atoms.
[0023] As examples of R when it is an alkyl-substituted phenyl,
there may be mentioned 2-methylphenyl, 3-methylphenyl,
4-methylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl,
3,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl,
2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 2,3-diethylphenyl,
2,4-diethylphenyl, 3,4-diethylphenyl, 2,5-diethylphenyl and
2,6-diethylphenyl.
[0024] As examples of R when it is an alkoxy-substituted phenyl,
there may be mentioned 2-methoxyphenyl, 3-methoxyphenyl,
4-methoxyphenyl, 2,3-dimethoxyphenyl, 2,4-dimethoxyphenyl,
3,4-dimethoxyphenyl, 2,5-dimethoxyphenyl and
2,6-dimethoxyphenyl.
(Substituents R.sub.1 and R.sub.2)
[0025] As the halogen atom represented by R.sub.1 and/or R.sub.2,
there may be mentioned F, Cl, Br, 0 and so forth. However, Cl and
Br are preferred, and Cl is particularly preferred.
[0026] As for the alkyl group represented by R.sub.1 and R.sub.2,
straight or branched alkyl groups containing 1-8 carbon atoms are
preferred, and straight or branched alkyl groups containing 1-4
carbon atoms are particularly preferred. As examples, there may be
mentioned methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,
sec-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl,
sec-hexyl, 2-ethylbutyl, n-heptyl, isoheptyl, sec-heptyl, n-octyl
and 2-ethylhexyl.
[0027] As for the alkoxyalkyl group represented by R.sub.1 and
R.sub.2, alkoxyalkyl groups containing 2-8 carbon atoms in total
are preferred, and alkoxyalkyl groups containing 2-4 carbon atoms
in total are particularly preferred. As examples, there may be
mentioned 2-methoxyethyl, 3-methoxypropyl, 4-methoxybutyl,
2-ethoxyethyl, 2-n-butoxyethyl, 2-n-propoxyethyl,
2-isopropoxyethyl, 2-n-butoxyethyl, 3-ethoxypropyl,
3-n-propoxypropyl, 4-ethoxybutyl, 4-n-propoxybutyl,
2-methoxy-2-ethoxyethyl and 2-ethoxy-2-ethoxyethyl.
[0028] As for the alkoxy group represented by R.sub.1 and R.sub.2,
straight or branched alkoxy groups containing 1-8 carbon atoms are
preferred, and straight or branched alkoxy groups containing 1-4
carbon atoms are particularly preferred. As examples, there may be
mentioned methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy,
isobutoxy, sec-butoxy, n-pentyloxy, isopentyloxy, neopentyloxy,
n-hexyloxy, isohexyloxy, sec-hexyloxy, 2-ethylbutoxy, n-heptyloxy,
isoheptyloxy, sec-heptyloxy, n-octyloxy and 2-ethylhexyloxy.
[0029] As for the alkoxyalkoxy group represented by R.sub.1 and
R.sub.2, alkoxyalkoxy groups containing 2-8 carbon atoms in total
are preferred, and alkoxyalkoxy groups containing 2-4 carbon atoms
in total are particularly preferred. Examples are 2-methoxyethoxy,
3-methoxypropoxy, 4-methoxybutoxy, 2-ethoxyethoxy,
2-n-butoxyethoxy, 2-n-propoxyethoxy, 2-isopropoxyethoxy,
2-n-butoxyethoxy, 3-ethoxypropoxy, 3-n-propoxypropoxy,
4-ethoxybutoxy, 4-n-propoxybutoxy, 2-methoxy-2-ethoxyethoxy and
2-ethoxy-2-ethoxyethoxy.
[0030] Preferred as R.sub.1 and R.sub.2 are a hydrogen atom, alkyl
groups containing 1-8 carbon atoms, alkoxyalkyl groups containing
2-8 carbon atoms in total, alkoxy groups containing 1-8 carbon
atoms, alkoxyalkoxy groups containing 2-8 carbon atoms in total, or
cyclic structures formed by R.sub.1 and R.sub.2 bound to each
other; particularly preferred are a hydrogen atom, alkyl groups
containing 1-4 carbon atoms, alkoxyalkyl group containing 2-4
carbon atoms in total, alkoxy groups containing 1-4 carbon atoms
and alkoxyalkoxy groups containing 2-4 carbon atoms in total.
[0031] As the ring structure formed by R.sub.1 and R.sub.2 bound to
each other, there may be mentioned a benzene ring, hydrocarbon ring
or oxygen-containing cyclic ring formed by R.sub.1 and R.sub.2
bound to each other, together with the benzene ring carbon atoms
bound to R.sub.1 and R.sub.2, respectively, preferably a benzene
ring, a hydrocarbon ring containing 5-7 carbon atoms, or an
oxygen-containing heterocycle containing 3-6 carbon atoms, more
preferably a benzene, cyclopentane or dioxolane ring. As examples,
there may be mentioned a benzene ring, cyclopentane ring,
cyclohexane ring, cycloheptane ring, dioxolane ring and dioxane
ring.
(Substituent R.sub.3)
[0032] When R.sub.3 is an unsubstituted alkyl group, it is
preferably a straight or branched alkyl group containing 1-18
carbon atoms, particularly preferably a straight or branched alkyl
group containing 1-8 carbon atoms. Examples are methyl, ethyl,
n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl,
isopentyl, neopentyl, n-hexyl, isohexyl, sec-hexyl, 2-ethylbutyl,
n-heptyl, isoheptyl, sec-heptyl, n-octyl, 2-ethylhexyl, n-decyl,
n-dodecyl, n-pentadecyl and n-octadecyl.
[0033] As the substituted alkyl group represented by R.sub.3, there
may be mentioned alkoxyalkyl groups, sulfoalkyl groups and
carboxyalkyl groups, among others. Alkoxyalkyl groups containing
2-8 carbon atoms in total are preferred, and those containing 2-4
carbon atoms in total are particularly preferred. As examples of
the alkoxyalkyl groups, there may be mentioned 2-methoxyethyl,
3-methoxypropyl, 4-methoxybutyl, 2-ethoxyethyl, 2-n-butoxyethyl,
2-n-propoxyethyl, 2-isopropoxyethyl, 2-n-butoxyethyl,
3-ethoxypropyl, 3-n-propoxypropyl, 4-ethoxybutyl, 4-n-propoxybutyl,
2-methoxy-2-ethoxyethyl and 2-ethoxy-2-ethoxyethyl.
[0034] Preferred as R.sub.3 are alkyl groups containing 1-8 carbon
atoms or alkoxyalkyl groups containing 2-8 carbon atoms in total
and, among them, alkyl groups containing 1-8 carbon atoms or
alkoxyalkyl groups containing 2-4 carbon atoms in total are
particularly preferred.
(Substituent L)
[0035] L is a substituted or unsubstituted alkylene group and forms
a ring together with three carbon atoms, namely the carbon atom
bound to X and the carbon atoms on both sides thereof. Preferred as
L are ethylene, propylene, butylenes, 2-oxapropylene,
2-thiapropylene, 2-methylpropylene and 2-tert-butylpropylene and,
among them, ethylene, propylene and butylenes are particularly
preferred.
(Substituent X)
[0036] The halogen atom represented by X includes F, Cl, Br and I,
among others. Cl and Br are preferred, and Cl is particularly
preferred.
[0037] The alkoxy group represented by X is preferably an alkoxy
group containing 1-8 carbon atoms, particularly preferably an
alkoxy group containing 1-4 carbon atoms. Examples are methoxy,
ethoxy, propoxy, butoxy, pentoxy, hexyloxy, heptyloxy and octyloxy,
among others.
[0038] The alkylthio group represented by X is preferably an
alkylthio group containing 1-8 carbon atoms, particularly
preferably an alkylthio group containing 1-4 carbon atoms. Examples
are methylthio, ethylthio, propylthio, butylthio, pentylthio,
hexylthio, heptylthio and octylthio, among others.
[0039] The aryloxy group represented by X is preferably a phenyloxy
group, which may optionally have an alkyl group containing 1-8
carbon atoms as a substituent, particularly preferably a phneyloxy
or methylphenyloxy. As examples, there may be mentioned phenyloxy,
methylphenyloxy and tert-butylphenyloxy.
[0040] The arylthio group represented by X is preferably a
phenylthio group, which may optionally have an alkyl group
containing 1-8 carbon atoms as a substituent, particularly
preferably phenylthio and methylphenylthio. As examples, there may
be mentioned phenylthio, methylphenylthio and
tert-butylphenylthio.
[0041] Preferred as the substituent(s) on the substituted amino
group represented by X are alkyl groups containing 1-8 carbon atoms
and a phenyl group and, among them, alkyl groups containing 1-4
carbon atoms and a phenyl group are particularly preferred. As
examples of X, there may be mentioned methylamino, ethylamino,
propylamino, butylamino, dimethylamino, diethylamino,
dipropylamino, dibutylamino, phenylamino and diphenylamino, among
others.
[0042] Preferred as X are a hydrogen atom, Cl, Br, an alkoxy group
containing 1-8 carbon atoms, an alkylthio group containing 1-8
carbon atoms, a phenyloxy group optionally having an alkyl group(s)
containing 1-8 carbon atoms as a substituent(s), a phenylthio group
optionally having an alkyl group(s) containing 1-8 carbon atoms as
a substituent(s), and a substituted amino group optionally having
an alkyl group(s) containing 1-8 carbon atoms and/or a phenyl
group(s) as a substituent(s). Particularly preferred are Cl, an
alkoxy group containing 1-4 carbon atoms, an alkylthio group
containing 1-4 carbon atoms, a phenyloxy group optionally having an
alkyl group(s) containing 1-4 carbon atoms as a substituent(s), a
phenylthio group optionally having an alkyl group(s) containing 1-4
carbon atoms as a substituent(s) and a substituted amino group
optionally having an alkyl group(s) containing 1-8 carbon atoms
and/or a phenyl group(s) as a substituent(s).
(Specific Examples of the Compound of the Invention)
[0043] Preferred specific examples of the polymethine ether
compounds of the invention as represented by the general formula
(I) are shown below. However, the compounds of the invention are
not limited to these. ##STR6## ##STR7## ##STR8## ##STR9## ##STR10##
##STR11## [Method of Producing the Polymethine Ether Compounds]
[0044] The polymethine ether compounds (I) of the invention can be
produced, for example, by reacting a polymethine compound
represented by the general formula (II) given below with an alkali
metal alkoxide or alkali metal aryloxide represented by the general
formula (III) given below in an organic solvent. ##STR12## (In the
formula, R.sub.1 to R.sub.3, L and X are as defined above and
Z'.sup.- represents an acidic residue.) MOR (III) (In the formula,
M represents an alkali metal and R is as defined above.)
[0045] In the above formula (II), Z'.sup.- represents an acidic
residue, for example F.sup.-, Cl.sup.-, Br.sup.-, I.sup.-,
BrO.sub.4.sup.-, ClO.sub.4.sup.-, BF.sub.4.sup.-, PF.sub.6.sup.-,
SbF.sub.6.sup.-, CF.sub.3CO.sub.2.sup.-, CH.sub.3CO.sub.2.sup.-,
CF.sub.3SO.sub.3.sup.-, CH.sub.3SO.sub.3.sup.-, benzenecarbonate,
benzenesulfonate, p-toluenesulfonate (hereinafter abbreviated as
TsO.sup.-, naphthalenecarbonate, naphthalenedicarbonate,
naphthalenesulfonate or naphthalenedisulfonate. In particular,
Cl.sup.-, Br.sup.-, I.sup.-, ClO.sub.4.sup.-, BF.sub.4.sup.-,
PF.sub.6.sup.-, SbF.sub.6.sup.-, CF.sub.3CO.sub.2.sup.-,
CF.sub.3SO.sub.3.sup.-, CH.sub.3SO.sub.3.sup.-, benzenecarbonate,
benzenesulfonate and TsO.sup.- are preferred, and ClO.sub.4.sup.-,
BF.sub.4.sup.- and TsO.sup.- are particularly preferred.
[0046] In the above reaction, M is an alkali metal such as sodium
or potassium.
[0047] As the organic solvent, there may be mentioned, among
others, alcohols such as methanol, ethanol, n-propanol, isopropanol
and n-butanol, ethers such as tetrahydrofuran and dioxane, esters
such as methyl acetate, ethyl acetate and butyl acetate, aromatic
hydrocarbons such as benzene, toluene and xylene, halogenated
hydrocarbons such as dichlormethane, trichloromethane,
dichloroethane and trichloroethane, and aprotic polar solvents such
as dimethylformamide, dimethylacetamide and dimethyl sulfoxide.
[0048] As for the quantity ratio between the compound represented
by the general formula (II) and the compound represented by the
general formula (III), the latter is generally used in an amount of
about 1-30 moles, preferably about 2-10 moles, per mole of the
former.
[0049] The organic solvent is generally used in an amount of about
2-30 liters, preferably about 5-20 liters, per mole of the compound
represented by the general formula (II).
[0050] The above reaction can smoothly proceed generally at about
0-100.degree. C., preferably at about 10-70.degree. C., and will be
generally complete in several minutes to about 10 hours.
[0051] After the reaction, the desired product can be readily
isolated by collection by filtration, followed by washing. It can
be purified with ease by the conventional purifying means, such as
recrystallization and/or column separation.
[0052] The above-mentioned compound represented by the general
formula (II) can be synthesized by the method described in Japanese
Kokai Publication 2000-226528, for instance.
[Method of Producing the Final Product Polymethine Compounds]
[0053] The polymethine compounds represented by the formula (IV):
##STR13## (wherein R.sub.1 to R.sub.3, L and X are as defined above
general formula (I) and Z.sup.- represents an acidic residue) which
have a desired Z.sup.-, can then be produced from the ether
compounds of general formula (I), for example, by reacting an ether
compound represented by the formula (I) with an acid containing the
desired Z in an organic solvent.
[0054] As Z.sup.-, there may be mentioned, among others, halogen
ions such as F.sup.-, Cl.sup.-, Br.sup.- and I.sup.-,
alkylsulfonate ions such as CH.sub.3SO.sub.3.sup.-,
CF.sub.3SO.sub.3.sup.- and C.sub.2H.sub.5SO.sub.3.sup.-,
arylsulfonate ions such as benzenesulfonate and p-toluenesulfonate
(hereinafter abbreviated as TsO.sup.-), naphthalenesulfonate ions
such as 2-naphthalenesulfonate ion,
1-hydroxy-4-naphthalenesulfonate ion and 2,3-naphthalenedisulfonate
ion, alkylcarboxylate ions such as CH.sub.3CO.sub.2.sup.-,
C.sub.2H.sub.5CO.sub.2.sup.-, C.sub.3H.sub.7CO.sub.2.sup.-,
CF.sub.3CO.sub.2.sup.- and C.sub.2F.sub.5CO.sub.2.sup.-,
arylcarboxylate ions such as benzoate ion and 3-hydroxybenzoate
ion, naphthalenecarboxylate ions such as 2-naphthalenecarboxylate
ion, 1-hydroxy-4-naphthalenecarboxylate ion and
2,3-naphthalenedicarboxylate ion, organoboron ions such as
triphenyl butyl borate ion and tetraphenyl borate ion, organometal
complex ions such as benzenedithiol nickel complex ion,
BrO.sub.4.sup.-, ClO.sub.4.sup.-, BF.sub.4.sup.-, PF.sub.6.sup.-,
SbF.sub.6.sup.-, etc.
[0055] The organic solvent includes alcohols such as methanol,
ethanol, n-propanol, isopropanol and n-butanol, ethers such as
tetrahydrofuran and dioxane, esters such as methyl acetate, ethyl
acetate and butyl acetate, aromatic hydrocarbons such as benzene,
toluene and xylene, halogenated hydrocarbons such as
dichlormethane, trichloromethane, dichloroethane and
trichloroethane, and aprotic polar solvents such as
dimethylformamide, dimethylacetamide and dimethyl sulfoxide.
[0056] The desired Z-containing acid may be a proton donor acid or
an electron acceptor acid.
[0057] The desired Z-containing proton donor acid includes, among
others, hydrohalic acids such as HF, HCl, HBr and HI, alkylsulfonic
acids such as CH.sub.3SO.sub.3H, CF.sub.3SO.sub.3H and
C.sub.2H.sub.5SO.sub.3H, arylsulfonic acids such as benzenesulfonic
acid and p-toluenesulfonic acid, naphthalenesulfonic acids such as
2-naphthalenesulfonic acid, 1-hydroxy-4-naphthalenesulfonic acid
and 2,3-naphthalenedisulfonic acid, alkylcarboxylic acids such as
CH.sub.3CO.sub.2H, C.sub.2H.sub.5CO.sub.2H,
C.sub.3H.sub.7CO.sub.2H, CF.sub.3CO.sub.2H and
C.sub.2F.sub.5CO.sub.2H, arylcarboxylic acids such as benzoic acid
and 3-hydroxybenzoic acid, naphthalenecarboxylic acids such as
2-naphthalenecarboxylic acid, 1-hydroxy-4-naphthalenecarboxylic
acid and 2,3-naphthalenedicarboxylic acid, HBrO.sub.4, HClO.sub.4,
HBF.sub.4, HPF.sub.6 and HSbF.sub.6.
[0058] The desired Z-containing electron acceptor acid includes,
among others, organoborate salts such as triphenyl butyl borate
salts and tetraphenyl borate salts, organic dithiol metal complex
salts such as benzenedithiol nickel complex salts, zinc chloride
and aluminum chloride.
[0059] As for the quantity ratio between the compound represented
by the general formula (I) and the acid containing the desired Z,
the latter is generally used in an amount of about 0.5-5 moles,
preferably about 1-2 moles, per mole of the former.
[0060] The organic solvent is generally used in an amount of about
2-30 liters, preferably about 5-20 liters, per mole of the compound
represented by the general formula (I).
[0061] The above reaction proceeds smoothly generally at a
temperature not higher than 100.degree. C., preferably
10-50.degree. C., and will be complete generally in several minutes
to about 10 hours.
[0062] After the reaction, the desired product can be readily
isolated by collection by filtration, followed by washing. Further,
it can be purified with ease by the conventional means, for example
by recrystallization and/or column separation.
EXAMPLES
[0063] The following examples illustrate the present invention more
specifically. These examples are, however, by no means limitative
of the scope of the invention.
Example 1
Production of a Polymethine Ether Compound (Specific Example
Compound (1))
[0064] A compound represented by the general formula (II) (each of
R.sub.1 and R.sub.2=hydrogen atom, R.sub.3=methyl, L=propylene,
X=Cl, Z'.sup.-=ClO.sub.4.sup.-; 3.79 g) and 1.76 g of a compound
represented by the general formula (III) (M=Na, R=methyl) were
added to 150 ml of methanol, the mixture was stirred at
20-25.degree. C. for 3 hours, the resulting crystalline precipitate
was filtered off, washed with methanol and recrystallized from
acetone to give 2.68 g of Specific Example Compound (1).
[0065] The elemental analysis data and melting point of this
compound were as follows. TABLE-US-00001 Elemental analysis
(C.sub.33H.sub.39ClN.sub.2O): MW = 515.13 C H N Calculated (%)
76.94 7.63 5.44 Found (%) 76.88 7.69 5.48 Melting point (.degree.
C.): 159-162.degree. C. (decomposition)
[0066] An IR spectrum of the compound obtained is shown in FIG.
1.
Example 2
Production of a Polymethine Ether Compound (Specific Example
Compound (2))
[0067] The procedure of Example 1 was followed in the same manner
except that the compound of general formula (III) as used was the
one with M=Na and R=ethyl (2.21 g), to give 2.82 g of Specific
Example Compound (2).
[0068] The elemental analysis data and melting point of this
compound were as follows. TABLE-US-00002 Elemental analysis
(C.sub.34H.sub.41ClN.sub.2O): MW = 529.15 C H N Calculated (%)
77.17 7.81 5.29 Found (%) 77.08 7.79 5.26 Melting point (.degree.
C.): 150-153.degree. C. (decomposition)
[0069] An IR spectrum of the compound obtained is shown in FIG.
2.
Example 3
Production of a Polymethine Ether Compound (Specific Example
Compound (6))
[0070] The procedure of Example 1 was followed in the same manner
except that the compound of general formula (II) as used was the
one with each of R.sub.1 and R.sub.2=hydrogen atom,
R.sub.3=n-propyl, L=propylene, X=Cl, Z'.sup.-=ClO.sub.4.sup.- (4.16
g), to give 2.80 g of Specific Example Compound (6).
[0071] The elemental analysis data and melting point of this
compound were as follows. TABLE-US-00003 Elemental analysis
(C.sub.37H.sub.47ClN.sub.2O): MW = 571.23 C H N Calculated (%)
77.80 8.29 4.90 Found (%) 77.88 8.35 4.92 Melting point (.degree.
C.): 97-100.degree. C.
[0072] An IR spectrum of the compound obtained is shown in FIG.
3.
Example 4
A polymethine Ether Compound (Synthesis of Specific Example
Compound (12))
[0073] The procedure of Example 1 was followed in the same manner
except that the compound of general formula (II) as used was the
one with R.sub.1=5-methoxy, R.sub.2=7-methyl, R.sub.3=methoxyethyl,
L=propylene, X=Cl, Z'.sup.-=BF.sub.4.sup.- (4.86 g) and that the
compound of general formula (III) as used was the one with M=Na and
R=ethyl (2.21 g), to give 2.90 g of Specific Example Compound
(12).
[0074] The elemental analysis data and melting point of this
compound were as follows. TABLE-US-00004 Elemental analysis
(C.sub.42H.sub.57ClN.sub.2O.sub.5): MW = 705.37 C H N Calculated
(%) 71.52 8.15 3.97 Found (%) 71.36 8.19 3.94 Melting point
(.degree. C.): 143-145.degree. C.
[0075] An IR spectrum of the compound obtained is shown in FIG.
4.
Example 5
A polymethine Ether Compound (Synthesis of Specific Example
Compound (16))
[0076] The procedure of Example 1 was followed in the same manner
except that the compound of general formula (II) as used was the
one with R.sub.1 and R.sub.2=5,6-methylenedioxy, R.sub.3=methyl,
L=propylene, X=Cl, Z'.sup.-=ClO.sub.4.sup.- (4.37 g), to give 2.83
g of Specific Example Compound (16).
[0077] The elemental analysis data and melting point of this
compound were as follows. TABLE-US-00005 Elemental analysis
(C.sub.35H.sub.39ClN.sub.2O.sub.5): MW = 603.15 C H N Calculated
(%) 69.70 6.52 4.64 Found (%) 59.56 6.49 4.58 Melting point
(.degree. C.): 175-177.degree. C.
[0078] An IR spectrum of the compound obtained is shown in FIG.
5.
Example 6
A polymethine Ether Compound (Synthesis of Specific Example
Compound (17))
[0079] The procedure of Example 1 was followed in the same manner
except that the compound of general formula (II) as used was the
one with R.sub.1 and R.sub.2=5,6-benzo, R.sub.3=methyl,
L=propylene, X=Cl, Z'.sup.-=TsO.sup.- (4.91 g), to give 2.54 g of
Specific Example Compound (17).
[0080] The elemental analysis data and melting point of this
compound were as follows. TABLE-US-00006 Elemental analysis
(C.sub.41H.sub.43ClN.sub.2O): MW = 615.25 C H N Calculated (%)
80.04 7.04 4.55 Found (%) 80.04 7.05 4.61 Melting point (.degree.
C.): 184-187.degree. C.
[0081] An IR spectrum of the compound obtained is shown in FIG.
6.
Example 7
A polymethine Ether Compound (Synthesis of Specific Example
Compound (22))
[0082] The procedure of Example 1 was followed in the same manner
except that the compound of general formula (II) as used was the
one with each of R.sub.1 and R.sub.2=hydrogen atom, R.sub.3=methyl,
L=ethylene, X=Cl, Z'.sup.-=ClO.sub.4.sup.- (3.70 g), to give 2.62 g
of Specific Example Compound (22). TABLE-US-00007 Elemental
analysis (C.sub.32H.sub.37ClN.sub.2O): MW = 501.10 C H N Calculated
(%) 76.70 7.44 5.59 Found (%) 76.62 7.50 5.59 Melting point
(.degree. C.): 205-207.degree. C.
[0083] An IR spectrum of the compound obtained is shown in FIG.
7.
Example 8
Synthesis of a Polymethine Compound
[0084] Specific Example Compound (12) (5.00 g) was added to 50 ml
of methanol, and 15 ml of a methanol solution containing 3.00 g of
pentafluoropropionic acid was added dropwise thereto with stirring
at 25-30.degree. C. After 2 hours of stirring at the same
temperature, the methanol was distilled off from the reaction
mixture using an evaporator, and 50 ml of ethyl acetate was then
added to the residue. The resulting crystalline precipitate was
filtered off, washed with ethyl acetate and dried to give 4.98 g of
a compound having the structure given below (yield: 85.2%).
[0085] The elemental analysis data, melting point, absorption
maximum wavelength (.lamda.max) and gram extinction coefficient
(eg) of this compound were as follows. TABLE-US-00008 Elemental
analysis (C.sub.43H.sub.52ClF.sub.5N.sub.2O.sub.6): MW = 823.3 C H
N Calculated (%) 62.73 6.37 3.40 Found ( % ) 62.81 6.40 3.38
Melting point (.degree. C.): 198-199.degree. C. .lamda.max: 822 nm
(diacetone alcohol solution) .epsilon.g: 2.75 .times. 10.sup.5 ml/g
cm
[0086] An IR spectrum of the compound obtained is shown in FIG. 8.
##STR14##
Comparative Example 1
A Hydroxy Compound and Production of a Polymethine Compound Using
the Same
[0087] As described in Example 1 in Japanese Kokai Publication
H11-1626, 15.0 g of a compound of general formula (II) with
R.sub.1=5-methoxy, R.sub.2=7-methyl, R.sub.3=methoxyethyl,
L=propylene, X=Cl, Z'.sup.-=BF.sub.4.sup.- was added to 150 ml of
DMF, and the mixture was stirred at 20-25.degree. C. for 0.5 hour
to effect dissolution. The solution was green, and the .lamda.max
of the DMF solution was 824 nm. To this DMF solution was added 4.8
g of a 50% aqueous solution of caustic soda, followed by 1.0 hour
of stirring at 25-30.degree. C. The color of the DMF solution
changed from green to yellowish brown (the .lamda.max of the DMF
solution changed to 434 nm and the absorption at 824 nm
disappeared).
[0088] The reaction mixture was poured into 1500 g of ice water,
and the resulting crystalline precipitate was filtered off, washed
with water and dried to give 12.51 g of an ocher compound.
[0089] This compound gave the following elemental analysis data and
was identified as a hydroxy compound of the formula (B) given
hereinabove. TABLE-US-00009 Elemental analysis
(C.sub.40H.sub.53ClN.sub.2O.sub.5): MW = 677.31 C H N Calculated
(%) 70.93 7.89 4.14 Found (%) 70.48 7.99 4.19
[0090] A 3.39-g portion of the hydroxy compound obtained was
dissolved in 35 ml of methanol, and 15 ml of a methanol solution
containing 2.12 g of pentafluoropropionic acid was added dropwise
thereto with stirring at 25-30.degree. C. After 2 hours of stirring
at the same temperature, the methanol was distilled off from the
reaction mixture using an evaporator, and 35 ml of ethyl acetate
was added to the residue. The resulting crystalline precipitate was
filtered off, washed with ethyl acetate and dried to give 2.28 g
(yield: 55.3%) of a compound having the same structure as the
product obtained in Example 8.
[0091] The absorption maximum wavelength (.lamda.max) and gram
extinction coefficient (eg) of this compound were as follows.
[0092] .lamda.max: 822 nm (diacetone alcohol solution)
[0093] .epsilon.g: 0.98.times.10.sup.5 ml/gcm
[0094] As compared with Example 8 in which a polymethine ether
compound of the invention was used, the yield of the polymethine
compound was low and the purity of the compound obtained was low
(.epsilon.g ratio relative to the compound of Example 8: 0.36).
INDUSTRIAL APPLICABILITY
[0095] The compounds of the invention are useful intermediates for
the production of polymethine compounds containing a desired
counter ion with high purity and in high yields.
[0096] The novel polymethine ether compounds are stable and can be
handled with ease and, when reacted with an acid, can give
high-quality polymethine compounds with the acidic residue as the
counter ion in high yields.
* * * * *